Method of coating leather with polymers containing cyclic t-amino groups and the resulting article



-contains certain cyclic t-amino groups.

United States Patent Mnmon F, eeimemxmmwim PQLY- M RS. CONTAINING CYCLIC TAAMINO GROUPS AND THERESULTIN'G ARTICLE This invention relates to coated leather vproducts and to processes for producing them. It isparticularly concerned with coated leathers having, cOmpositemulti-ilayer coatings which have improved adhesion to the leather and to each other and excellent softness and flexibility even under extremes of cold and heat.

vor 'acryldnitrile;@acrylamide, or methacrylamide, and N- e U. S. Patent 2,204,520 discloses a procedure for apply- I.

ing aqueous dispersions of emulsion-polymerized;.acrylic acid esters or the like to leathers. Such dispersions in practice are frequently provided with pigments and are generally covered with one or more final .lacqu'er :top coats. The aqueous dispersion serves to fill imperfections and to level the surface of the leather and to improve the adhesionbetween any lacquer-top coatsapplied and the leather.

The coatings obtained from the aqueous dispersions disclosed in the patent provide good adhesion to many leathers :and particularly to snuffed,- bulle'd, and=split leathers. However, .on .some types ofifull grain leathers such coatings have poor adhesion. This poor adhesion .is' particularly noticeable on leatherswhichhave been subjected ate-certain types of fatliquoring, tsuehias sperm oil, or which have acquired 'suchta large amount of .fatty deposits on the surface of the leather duringfatliquoring as to in effect provide aresist to aqueous coating compositions.

.It has now been discovered that improved :adhesion may be obtained between the leather and polymers applied to it bymeans of an aqueous vehicle if the polymer In accordance with the present invention, it has been found that the application of aqueous dispersions .of certain :resins containing cyclic t-amino .groups .to the leather provides improved adhesion to full grain leathers as well-as'to biified and split leathers and also improves the resistance to 'scu'ffing resulting from rubbing action against the finished leather surface as well as improvement in resistance to wet m'ol'ding operations.

Toim'part the improved qualities in the finished lea'thers in accordance with the present invention, the leather is coated with an aqueous dispersion of a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 3% to 50% by weight of at least one monomeric compound selected from 4-Vinylpyridine and 2-methyl-5-vinylpyridine.

The improved adhesion obtained with such cop'oly'm'e'rs could not be predicted; similar copolymers of 2-vinylpyridine and 5-ethy1-2-vinylpyridine do not show the-improved adhesion that is obtained with copolymers of the 4-vinylpyridine and Z-me'thyl-S vinylpyridine above.

The polymers must not be water-soluble. Therefore, it is necessary to copolymerize the vinylp'yridine with at least one other copolymerizable monoet hylenically unsaturated monomerwhich is of a character thatwill'render the final copolym'er insoluble in water. Also, it"i's preferable from the cost standpoint, and for controlling properties, such as flexibility, to copolymer'i'z'e the vinylvethylenieally unsaturated group that may be'cbp'olyine'p ice . 2 pyridine with more than 50% of one or more cheaper and more readily available 'comonomers; Preferred cornposi't-ionspf theinve'ntion are; therefore; those c'opoly- .mers of fr'om 5% 1o 15% "of the viriylpyridiri'e monomer er-monomers; the balance of the copblyrnei' being formed of otherless expensive coinonomers:

Other :polymerizable compounds containing a. single i-zed with t-hevinylpyr'idine monomer :to prbdu'ce bxna y, ternary, etc. copolymerseinclude the esters of acrylic acid or :methacrylic. acid .or the dimer ofmethac'ryli'c acidwith monohydric alcohols such as methyl, ethyl, utyl, oetyl, dodecylg cyclohexyl, .cyanOethyLJbenZyI, phenylethyl, and thelikeudiesters o'f ita'conic acid an'd the "above alcohols; esters of 'maleie; ffumaric, "or citra'conic acids with the above alcohols; vinyl esters of 'carb'oxyli'c acids =si1cli-as acetic, npropionic, butyric, and the like; vinyloxyalkyl ,esters such as -;,vlnyloxyethyl acetate; :e'tc.'; vinyl 'etliers and sulfides such -as ethyl vinyl ether, ethyl vinyl sulfide, bu'tyl vinyl ether, 'octyl vinyl *ether; methacryloriitrile v alk yl-su'hsti'tuted amides of these types; vinyl toluene, vinYlnapht-haIenes, suehz-as =4-1chloro-1-vinyl naphthalene,

, and styrene,

The emulsifiers or disp'ersingagents that:rnay be gs-5a for preparing the monomeric emulsions before co'polyf-merizationor =dispersions-of =the polymer after polymer- ..i zation gnajy be .of anionic, cationic; sor non-ionic type or a mixtureof two ttypes may be used. 30

, Suitable anionic dispersing agentsin'elude' the :liig' 'he'r fatty alcohol sulfates; suchias' sodium 'lauryl sulfate, amylarylsultouates, e. :g'. sodium orxpdtassium 'isopropylbeiivzene sulfonates oriisopropyl naphthalene "sulfonates'; alkali metalthigher alkyl 'sulfosnccin'ates; re. :g.'-sodium' o ctyl 'siilfosuccinate, sodium N methyl-Nqialmitoyltaurate', sodi- .um oleyl isothio'nate, alkali metal salts or alkylar'ylpolyethoxyethanol sulfates or 'sulfonates, e g. sodihn'i t-octyl- .phenoxypolyethoxyethyl "sulfate having 1 to 5 oxyethyl- 40 .ene iunits.

'dinium chlorides, cetyl dim'ethyl amine ae'etate, arid arrivi- Suitable cationic dispersing agents include 'Iauiylpyri- 'dimethylbenzylammonium' chlorides in whi h the alkyl group has from 8 to 1'8 "carbon atoms; such as o'c't-yl, decyl, 'dodecyl, or octadecyl; 't-octylpherioxyeth'oxyethoxy dimethylbenzylammonium chloride. I v

' Suitable non-ionic dispersin'g'agents inc'lude'th'follow- ,ing: ;alkylphenoxypolyethoxyethanols having alkyl groups of about seven :to eighteen carbonato'ms andfi to '66 or more oxye'thylene' units, such as *heptylphenoxyp'olyethoxyethanols, octylphenoxypolyethoxyethanols, methyloctylphermxypolyethoxyethanols, nonylphenoxypolyeth'oxyeth anols, -dodecylphenoxypolyethoxyethanols and the like; polyethoxyethan'ol derivatives of methylene linked alkyl phenols; sulfur-containing agents such' as those made by condensing 6 to-60 or more moles of ethylene oxide with nonyl-,jdodecyl, 't'etradeeyl, t-dodecyl', "and the like mercaptans or with alkylthiophenols having alkyl groups of six to fifteen carbon atoms; ethylene oxide derivatives of long-chained carboxylic acids, su'eh as lauric, myri'stic, palmitic, oleic, and the like or mixtures of acids suchfas found in tall oil containing 6 to 6'0 'oxyethylene units per momenta-analogous ethylene oxide umdenates of tone chained alcohols, such as octyl, aeeyr 'lauryl; or eay'l alcohols, ethylene oxide derivatives of etheritie'd or -eisterifie d polyli'ydroxy compounds having a hydrophobic hydrocarbon chain, such as sorb ita n: monostearatel containing' 6 to 60 oxye'thylene units, etc,; alsoethyle'ne oxide condensates of-long-chainior' branched chain'amine's, such as dotlecylamine, hexadecylamin'e', and octadecylamine, containing 6 to 60 oxyethylene groups; block copolymers of ethylene oxide and propylene oxide comprising a hydrophobic propylene oxide section combined with one or more hydrophilic ethylene oxide sections.

Particularly valuable resin dispersions are obtained by emulsifying a mixture of (a) one or more of the vinylpyridine monomers above and (b) one or more monomeric esters of acrylic, methacrylic, or itaconic acid or mixtures of theseacids in water and polymerizing the mixture while it is in the emulsified form. The monomeric esters which have proven to be most satisfactory are the alkyl esters in which the alkyl group contains one to eight carbon atoms and which are exemplified by the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, isoamyl, tert-amyl. hexyl, heptyl, n-octyl, and 2-ethylhexyl acrylates, methacrylates, and itaconates.

The polymerizable emulsions can be prepared at temperatures from C. to about l00 C., but intermediate temperatures are much preferred. Thus, when the preducing agents such as a combination of potassium persulfate and sodium metabisulfite. Other suitable peroxidic agents include the per-salts such as the alkali metal and ammonium persulfates. and perborates, hvdrogen neroxide, organic hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide, and esters such as tert-butyl perbenzoate. Other reducing a ents include water-soluble thiosulfates, hydrosulfites, tertiary amines, such as triethanolamine, thiourea, and the salts, such as the sulfates, of metals which are capable of existing in more than one valence state such as cobalt, iron, nickel, and copper. The most convenient method of preparing the dispersions of copolymers comprises agitating an aqueous suspension or emulsion of the mixture of copolymerizable monomers and a redox catalytic combination at room temperature without the application of external heat. The amount of catalyst can vary but for purposes of efficiency from 0.01% to 3.0%, based on the weight of the monomers, of the peroxidic agent and the same or lower proportions of the reducing agent are recommended. In this way, it is possible to prepare dispersions which contain as little as 1% and as much as 60% or even more of the resinous copolymer on a weight basis. It is, however, more practical, and hence preferred. to produce dispersions which contain about 30% to 50% resinsolids.

Preferably a pigment is introduced into the aqueous coating dispersion and the amount of pigment introduced may vary from that equivalent to about to 150% by weight of the polymer. Generally, the pigment is first dispersed in'water (to a concentration of about 30% to 45%) by means of a non-ionic or anionic dispersing agent or a mixture of both types thereof. Any of the dis ersing agents mentioned above may be used. In addition, a small amount of a protective colloid may be included to thicken and/or stabilize the suspension and prevent the pigment from settling out. Examples of such colloids include methyl cellulose, hydroxyethyl cellulose. polyvinyl alcohol, sodium, potassium or ammonium alginates, am-

monium or alkali metal salts of homopolymers and comay be applied to the leather at a solids concentration of 10% to 50% (including the weight of polymer and pigment, if any). It maybe applied by any suitable equipment such as by brushing, swabbing, or spraying onto the leather. After application of the dispersion, it may be dried on the leather either by drying in the ambient atiosphere or at somewhat elevated temperatures up to 50 C. The amount of copolymer applied on the leather varies widely with the type of leather and the ultimate finish desired. For most purposes, the amount applied per thousand square foot of the leather may vary from 1 to 15 pounds.

It is believed that the improved adhesion obtained on leather by the application of the vinylpyridine polymers containing cyclic t-amino groups is attributable to some chemical or physico-chemical reaction between such groups and the protein molecules of the leather or with the tanning agent or fatliquor deposit on the leather, or possibly on some joint reaction with two or more of these substances. However, it is not intended that the invention be limited by any particular theory of operation.

For some purposes, the leather product carrying the single coating obtained from the application of the aqueous dispersion of the vinylpyridine polymer with or without pigment may serve as a suitable finished product. For example, this may be the case when'it is desired only to impart a water-repellent surface to the leather and the polymer applied by the aqueous dispersion is of highly hydrophobic character as the result of the presence of a long-chain hydrocarbon group in the comonomer. However, in many cases, it may be desired to apply one or more additional coatings of a lacquer type over the coating obtained from the aqueous polymer dispersion. Any suitable lacquer composition may be applied such as those which comprise as the film-forming material an addition polymer of vinyl, acrylic or related types, a cellulose derivative such as a nitrocellulose or cellulose organic acid esters such as cellulose acetate, cellulose acetate butyrate or the like. The lacquers may comprise a plasticizer if the film-forming agent itself is not adequately flexible. When a single lacquer top coating is applied over the coating obtained from the aqueous polymer dispersion, it may be clear, it may be dulled by a filler or other suitable agent, such as a water-insoluble soap, e. g. aluminum stearate, or various silicas, or it may be colored with a white or suitably colored pigment. Preferably at least two lacquer top coatings are applied in succession over the coating obtained from the aqueous dispersion. When two such lacquer coatings are applied, the first is preferably pigmented to augment the color and covering obtained by the pigment, if'any, applied by the coating from the aqueous dispersion and the second lacquer coating is preferably clear or merely dulled to provide the glossiness or flatness desired in the final surface.

Each of the subsequently applied coatings should be dried before any later coating is to be applied and drying may be effected as before either at normal room temperature in the ambient atmosphere or at somewhat elevated temperatures up to 50 C.

If desired, the leather may be embossed after the coating applied in the aqueous dispersion has been dried on the leather and before subsequent lacquer coatings are applied, or embossing may be applied at any time after subsequent coatings are applied but preferably before the last or final coat is applied. Such embossing should, in all cases, be applied to the'coated leather in a dry condition.

As the vinyl or acrylic addition polymer that may be used for the film-forming component of the subsequently applied lacquer or lacquers, there may be used one or more homopolymers or copolymers of the following monoethylenically unsaturated compounds: vinyl chloride, vinyl acetate, vinyl propionate, vinylidene chloride, esters and nitriles of acrylic and methacrylic acids such as acrylonitrile, methacrylonitrile, and the alkyl esters of acrylic or methacrylic acid in which the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl,

hta tyl and act-wwe tw th ahove .hQ I PQ Yr mm and cqpd yme y psily nyl a t t s s ch as poly iny acetal t lf, Po y ny 'bmyr or par ially hyd o yz o op lyme a d c ph yinets inyl a et t i yl propionateor of acrylic and methacrylic esters may be 'u u h comp ds c ntain reactive hyd QXy an carboxyl groups. Other polymers containing reactive groups may be used provided the polymers do not contain suflicient reactive groups to render them insoluble in the ,organicsolvent employed. Such polymers include the copolymers containing up to 59 mole percent of fi-hydroxyethyl vinyl ether or of .fi-hydroxypentyl vinyl ether, up to 50 mole percent of aminoethyl acrylate, amino-ethyl vinyl ether or N-methylor N-ethylaminoet yl vinyl h r, or up to 30. 1 percent of a viny pyridine, such as Z-Vinyl-pyridine, or 4-vinylpyri-dine, or of an am h as rylamid methacry mid .N- methyl acrylamide, or of an acid, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and the dimer or trimer of methacrylic acid, or itlie like.

'Whena plasticizer i used, it may be a polyestet, :Polyam de, or p yester a ide s a may e o a n dbyth c n n a on react on o a as c th polq or polya Mo e p t cula y, th pla ti zc hich m y rmed Po y e nlas e ze m y so a ned byreacting combinations of materials of the general types noted below:

I 'Glycols (or other polyols) and dibasic acids n Amino alcohols and dibasicacids I II Glycols, diamines and dibasic acids IV Glycols, amino alcohols and dibasic acids V Amino alcohols, diamines and dibasic acids VI Amino acids,-glycols and dibasic-acids V-II Amino acids, amino alcohols and dibasic acids 'ZV I-II Amino alcohols, glycols and dibasic acids I'X Amino alcohols, dibasic acids and hydroxycarboxylic acids.

{It isadvantageous to use a small excessof the alcoholic-- .hexahy t rep t a ic. p-ph hy e -di c ti hdt etq dicarboxylic acids.

am n l oh l ha g at l a t o hydro n-awn a ac d t the am n n n a om m y be emp yed inc din ar m t alc hols, -py o y e hy vvayla ine, ;4.-hydroXymethyl-4-.aminomethyldiphenyl land ;p,,atninopheuylethyl alcohols; aliphatic amino alcohols, e. g. S-arninopentanol-l:-6-amino-S-methylhexanol-l,4(p- :arninophenyl) cyclohexanol, hydroxyethoxyethoxyethyl --amine and .N-. (,6-aminoethyl-) N-(omega-hydroxyhexybaniline. I

w'Ihe-preferred amino alcohols are offormula HO-R-NH :where "R represents saturated divalent hydrocarbon radicals with a chain length of at least two carbon atoms. Amino alcohols which fall within this group include etha-nolamine, '3 aminopropanol, 4 arninobutanol, 6 -arninopropanol, =4-amin0butanol, 6-aminohexanol, and

IO-aminodecanol.

Any diamine may -be employed, which contains at jleast one' hydrogen atom attached to each amino nitrogen atom. The preferred diamines areof formula NHgRNl-I; whe e R ep e a u te d lch yd o a ph rad sal w a c a n len -Q a leas tw .fit'UbQD s. y d inc, .he ame hyl n diarhi e, zmethy 'hexamethylenediamihc, and decarnethylenediamine. ,How-

-rnay comprise a "mixture of several types.

than others.

12-hydroxystearic acid.

Any pol-yrnerizable rnonoaminomonocarboxylic acid or esterforming derivative thereof may -be employed including -6-ami-noeaproic, 9-aminononanoic, and l-l-aminoundecanoic, and lZ-aminOste Iic acids, caprolactum, etc.

The organic solvents that may be used include ketones such as acetone, methyl ethyl 'ketone and dioxane; 'hydrocarbonssuch as xylene, toluene, benzene as well as parafiinic or naphthenic types such as solvent naphthas,

esters such asethyl, propyl, =butyl and amyl acetate as well as ethoxyethyl acetate, butoxyethyl acetate and the like, or others-such as butyl ethyl ether. The solvent If a polyisocyanateis used as suggested hereinafter, a solvent should be of a-type which does notcontain an active hydrogen.

The pigments that may be employed in the lacquers or the-aqueous copolymer dispersion or inboth of these media include red iron oxide, chrome green, rnolybdate chrome orange, -phthalocyanines, such as copper phthalocyanine, titanium dioxide, lithopone, chrome yellow, n1- .tramarine blue, red cadmium, yellow cadmium, organic toners and lakes, and so on.

It has :been found that the adhesion between the leather and the coating theregmespecially when several layers are applied to the leather; is even' further vproved when a polyisocyanate is applied to the coated leather at any time after the aqueous polymer dispers ion has been dried on the leather. For example, the poly- -.iso-cyanate may be applied-by spraying or swabbing' over the dried polymer coating obtained from the aqueol s dispersion. :I-t may also be applied as ,a component in any of the subsequently applied "laequers or it rnay ,be applied to the dried coated "leather after any of ,the' su bsequently applied lacquers. Preferably, if a polyiso- 'cyanate is employed, --it-is incorporated in the first lacquer coating applied over the polymer coatingobtainecl from the :aqueous dispersion. I

Examples of the polyisocyanates that-may :be employed include especially the hydrocarbon polyisocyanates such as ethylene diisocyanate, tetrarnethylene "diisocyenate, -hexarnethylene diisocyanate, decamethylene cliisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanates, benzene 1:3:5-triisocyanate, toluene-2 4 6-triisocyanate, ethylbenzene-2 4 6-triisocyanate, monochlorohenzene-2 :4 fiwtriisocyanate, triphnylmethane-.4:4:4" triisocyanate and diphenyl-2:4: 4-triisocyanate, toluene-2,4-diisocyanate, AAHdiisocyanato-biphenyl, 3,3-dimethyl-4,4'-diisocyanato-biphenyl, and 3,3- dimethoxy-4,4'-diisocyanato-biphenyl. The -polyisocyanates have various reactivities, some being much slower For example, diphenylmethane-4,4-diisocyanate is highly reactive whereas the 3,3-dimeth o xy- .4,4'-diisocyanato-biphenyl is relativelyslow. To com- ;pensate for the difierence in reactivity, the proportion added may be increasedfor the slower ones and decreased for the faster ones or basic catalysts, such .as tertiary amines may be included, especially with the slower ones. Mixtures of the polyisocyanates may be used of which .preferred combinations are mixtures of -toluene-2,4-diisocyanate with either 3,3'-dimethylr4,4i-diisocyanatmbiphenyl or 3,3'-dirnethoxy-4,4' diisocyanato-biphenyl.

the plasticizer in the several. coatings.

7 t reacted. By so leaving the active isocyanate groups the drying of subsequent lacquer coatings provides the opportunity for reactive combination of isocyanate groups with any reactive groups that may be present in such subsequently applied lacquers.

It appears that, when a polyisocyanate is used, the improved adhesion between the several layers of the coating and between the leather is at least partially attributable to some reaction between the polyisocyanate, the leather, the film-forming component and possibly It should be understood, however, that the application to the leather of the aqueous dispersions of the polymers of 4-vinylpyridine and Z-methyl-S-vinylpyridine imparts improved adhesion between lacquer coatings and the leather and shows improved adhesion between the leather and the polymer deposited from the aqueous dispersion. This adhesion is for most purposes fully adequate even without the employment of a polyisocyanate. The application of the polyisocyanate, however, may be desirable to obtain even better adhesion for some particular purposes andhas also the advantages of increasing the dryness or slipperiness of the top surface of the coated leather. When two lacquer coats are applied over the coating obtained from the aqueous polymer dispersion, the first of such lacquers preferably has the following composition: from 20 to 200 parts by weight of plasticizer, if present, per 100 parts of the addition polymer or cellulose ester; from S to 150 parts by weight of a pigment or mixture of pigments per 100 parts of the film-forming component; from 1% to 65% by weight of a polyisocyanate, if used, this percentage being based on the sum of the weights of the plasticizer and film-forming component. The amount of solvent employed may be such as to provide a solids concentration (that is materials other than the solvent themselves) of 2% to 20% by weight. The final lacquer coat is usually an unpigmented solution (either clear or dulled by an inert delustering filler) of the plasticizer and film-forming component, either or both of which may be the same as or different from the respective plasticizer and film-forming component of the first lacquer coat. When both lacquer coats contain plasticizer, the proportion in the final coating is somewhat less in proportion to the film-forming component than the proportion used in the first lacquer coating. Generally, it is within the proportion of 15 to 80 parts per 100 parts of the film-forming component.

In the following examples, which are illustrative of the invention, parts and percentages are by weight unless otherwise noted: 7

Example I (a) A dispersion of a copolymer was prepared by emulsifying 95 parts by weight of ethyl acrylate with 5 parts of 4-vinylpyridine in about 300 parts by weight of .water with about 2 parts by weight of sodium lauryl parts of water by means of two parts of a suitable dispersing agent, such as a mixture of equal parts of sodium lauryl sulfate and t-octylphenoxypolyethoxyethanol containing about oxyethylene units in combination with /2 part ofa suitable protective colloid, such as methyl cellulose, and the mixture was added to 100 parts of the copolymer dispersion of part (a) hereof. pigmented dispersionwvasswabbed on several pieces of The resulting 7 a full grain upholstery leather and dried at 50 C. The coating exhibited excellent adhesion to the leather.

' (c) The procedure of parts (a) and (b) hereof is repeated. except the 4-vinylpyridine is omitted so that a dispersion of a .homop'olymer of ethyl acrylate is produced and applied to the full grain upholstery leather. The coating on .the leather could be pulled off the leather intact. a r

(d) The procedure of parts (a) and (b) hereof is repeated except the 4-vinylpyridine is replaced with 2-vinylpyridine. The coating obtained, like .that obtained in part. (0) hereof, could be pulled ofi the leather intact.

Example 2 (a) A mixture of 40 parts of red iron oxide, six parts of a plasticizer consisting of a polyester obtained by the reaction of sebacic acid with anexcess of propylene glycol and having a number average, molecular weight of about 4,000, 2.9 parts by weight of a copolymer of vinyl chloride and 10%' vinyl acetate having a number average molecular weight of about 40,000, 6.1 parts ethoxyethyl acetate, 25 parts of methyl ethyl ketone and 20 parts of a petroleum solvent consisting of a mixture of aromatic, naphthenic, and aliphatic hydrocarbons is ground in a ball mill for 24 hours to form a pigment dispersion.

(b) A solution is also formed from 3.1 parts of the 'same plasticizer as above and 5.0 parts of the same vinyl copolymer in 10 parts of ethoxyethyl acetate, 44 parts of methyl ethyl ketone and 34.9 parts of a hydrocarbon solvent largely consisting of xylol.

(c) The solution of part (b) hereof is then mixed with the milled pigment dispersion of part (a) hereof in the ratio of 90 parts of the former to 10 parts of the latter. The resulting dispersion is applied to a piece of the coated leather obtained in part (b) of Example 1 and dried at 50 C. for about three hours.

(d) Then a clear coating is applied to the coated leather obtained in part (c) hereof by spraying a solution containing about 1.5% of the same plasticizer (of part (a)) and 5% of the same vinyl copolymer (of part (a)) in a solvent mixture composed of- 10% of ethoxyethyl acetate, 55% methyl ethyl ketone and 35% of a hydrocarbon composed largely of xylene. After applying the clear coating by spraying, it was dried at 50 C. The final coated leather had a glossy color and was soft and flexible but free of any draggy feel.

7 7 Example 3 (a) The procedure of Example 2, parts (a) through (d) is repeated except that 3.0 parts of toluene-2,4-diisocyanate was added to the solution of part (b) thereof. The resulting leather has a drier feel, shows excellent adhesion between the coatings and also between the leather and the several coatings, and is even more resistant to wet molding operations than that obtained without the diisocyanate in Example 1.

(b) The procedure of Example 2, parts (a) through (d) is repeated except that 3.0 parts of toluene-2,4-diisocyanate is added to the solution of part (b) thereof and the dispersion obtained in part (0) thereof is applied to the leather obtained in part (c) of Example 1 wherein the full grain upholstery leather is coated with a homopolymer of ethyl acrylate. The adhesion of the coatings to the leather is fair but special precautions are needed during wet molding operations to prevent damage to the finished leather.

(0) The procedure of Example 2, parts (a) through (d) is repeated except that 3.0 parts of toluene-2,4-diisocyanate is added to the solution of part (b) thereof and the dispersion obtained in part (d) of Example 1 wherein the full grain upholstery leather is coated with a copolymer of 2-vinylpyridine. The adhesion obtained between the coatings and the leather is fair and comparable to that obtained in part (b) hereof.

prises a pigmented water-insoluble linear polymerof about 5% by weight of 2-methyl-S-vinylpyridine, 80% of ethyl acrylate, and 15% of n-butyl acrylate, and,

superimposed on said layer, a pigmented lacquer coating 14. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of monoethylenically unsaturated mole cules comprising 3% to 50% by weight of at least one monomeric compound selected from 4-vinylpyridine and 2-methyl-5-vinylpyridine, and then drying the coated leather.

15. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of about 5% of 4-vinylpyridine, 80% of ethyl acrylate, and of n-butyl acrylate, and then drying the coated leather.

16. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of about 5% of 2-methyl-S-Vinylpyridine, 80% of ethyl acrylate, and 15% of n-butyl acrylate, and then drying the coated leather.

17. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of about 5% of 4-vinylpyridine and 95% of ethyl acrylate, and then drying the coated leather.

18. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble ilinear polymer of monoethylenically unsaturated molecules comprising 3% to by weight of at least one having a coating'thereon comprising a water-insoluble linear p olymer'of monoethylenically unsaturated molecules comprising ethyl acrylate, 15% n-butyl acrylate and 5% by weight of 4-vinylpyridine;

21. The method of finishing full-grain leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising 3% to 50% by weight of at least one monomeric compound selected from 4-vinylpyridine and 2-methyl-5-vinylpyridine, and then drying the coated leather.

References Cited in the file of this patent UNITED STATES PATENTS 2,204,520 Walker et al. June 11, 1940 2,430,479 Pratt et al. Nov. 11, 1947 2,615,826 Mallory et al. Oct. 28 1952 2,694,688 Hughes Nov. 16, 1954 2,702,763

Pritchard Feb. 22, 1955 

18. THE METHOD OF FINISHING LEATHER COMPRISING APPLYING THERETO AN AQUEOUS DISPERSION OF A WATER-INSOLUBLE LINEAR POLYMER OF MONOETHYLENICALLY UNSATURATED MOLECULES COMPRISING 3% TO 50% BY WEIGHT OF AT LEAST ONE MONOMERIC COMPOUNDS SELECTED FROM 4-VINYLPYRIDINE AND 2-METHYL-5-VINYLPYRIDINE, THEN DRYING THE COATED LEATHER, APPLYING THERETO A LACQUER, AT LEAST ONE OF SAID DISPERSION AND LACQUER BEING PIGMENTED, AND DRYING THE LACQUER. 